Alkyl-and aryl-esters of alkyl benzenesulfonic acids



Patented Nov. 1, 1949 UNITED STATES PATENT or 2,4 6,417 FICE ALKYL- AmiARYL-ESTERS or ALKYL nanznnssunromc ACIDS Dona-id n. Jackson, as WilliamK. was.

Wyandottc, Mich, assignors to Wyandotte v Chemicals Corporation,corporation of Michigan Wyandotte, Mich., a

No Application January 10, ms,

, SeriaiNo.'2,815 I The present invention relates to new and valuablechemical compounds comprising aikyland aryl-esters of alkylatedbenzenesulfonic acids; and to the process for the preparation thereof.

In the copending U. S. patent applicationgof 11 Claims. (L260-458) droxycompound such as an phenol. The alkylor aryl-, alkyibenzenesulionate isobtained in good yield, the final esterifl- Donald R. Jackson, SerialNo. 728,389, filed February 13, 1947, said Jackson being co-applicantherein, there is discloseda novel process for synthesizing monohydroxyand poiyhydroxy aliphatic alcohol esters of benzene-I and naphthalenesulfonic acids. Such process involves the reaction of benzeneornaphthalene sulfonyl chloride with the aliphatic alcohol in theesteriflcation reacaryi sulfonyi chloride is alkyiated in the benzenenucleus prior to such esteriflcation reaction that new alkylatedbenzenesulfonic esters, having ex, ceptional properties as plasticizingagents can be cation reaction being continued under conditions involvingthe presence of at least 200% molar ex cess of 35-50% strength causticalkali, a reaction temperature of 35-50% C. and not over a 2:1 moi ratioof aliphatic alcohol or phenol to the aihlat- I tion. We have nowdiscovered that where the made according to the operating conditions ofthe process of the aforesaid copending Jackson application.

The alkylbenzene sulfonic acid esters of our invention' are illustratedby the following general type formula:

where: is an alkyl group containing 1 to 8 carbon atoms, which may bederived from both straight chain and branched chain acyclichydrocarbons, and A is an alkyl or aryl group derived from monoandpolyhydroxy acyclic and .cyclic hydrocarbon compounds. such as thenormal alcohols, the aikylene glycols, and the phenols and homologuesthereof.

Specific examples of the alkylbenzene sulionic acid esters of'ourinvention are:

n-Butyl octylbenzenesulfona Phenyl octylbenzenesulfonate 1 Phenylxylenesuifonate n-Butyl xylenesulfonate n-Butylsec-butylbenzenesulfonate Phenyl sec-butylbenzenesulfonate In itsbroader concept, our invention involves the esterification of analkyibenzene sulfonic acid with a monoor polyhydroxy hydrocarboncompound. We prefer, however, to utilize the synthesizing procedurehereafter described;

The new chemical compounds: n-butyl octylbenzenesulfonate and phenyloctylbenzenesulfonate, in particular, possess unusual properties asplasticizing agents, particularly when used for such purpose withplastic materials of the polyvinyl chloride type.

Briefly outlined, the synthesizing procedure of our invention involvesthe aikylation of benzene,

. the chlorsulfonation of the alkylated benzene,

followed by the reaction "of the resultant alkylbenzenesulfonyl chloridewith a hydrocarbon hyed benzenesulfonyl chloride. Preferably, the excessof caustic alkali is in the range of 3001100% molar excess, viz., 4-12mols of NaOH per mol of alkylbenzenesulfonyl chloride.

The following examples will enable those skilled in the at more readilyto understand and prac-- tice our invention, such examples being setforth by way of detailed illustrations, but not necessarily inlimitation of the scope of the invention.

A. lreparatioh of octylbenzene .water followed by a wash with a10%sodium carbonate solution. After the sodium carbonate wash. themixture waswashed 3 times with water until neutral. The benzene was thenstripped by distillation from a 3 liter flask up to a maximum pottemperature of 205 C. After stripping off the excess benzene (1,238grams), the distilland was then subjected to a vacuum distiliation at a2 mm. Hg pressure andthrough a 10" long 29 mm. diameter glass helixpacked column. There was obtained 778 grams of octyibenzene,representing 82% theoretical yield, on

the basis of the n-octanol starting product. B. Preparation ofoctylbenzenesulfonyl chloride Octylbenzene obtained from part (A) ofthis example, in the amount of 768 grams. or 4.04 mols, was reacted with1,404 grams of chlorsulfonic acid -(9 mols) the latter being graduallyadded over .a period of approximately 1' hour and the reac- 'tiontemperature maintained in the range of 1322f C. After completion of thechlorsulfonic acid addition, stirring of the reaction mass was continuedfor 22 minutes and thema'ss drowned.

in about 2 kilograms ofice. Thefre'suitant mixture was then furtherdiluted with about 6 liters of water in a battery jar. Theoctylbenzenesuialiphatic alcohol or fonvl chloride settled out rapidly:a'na theweter Y perature being maintained in the range of -13 I C.After the'completion of such addition, stirlayer was decanted.The-octylbenzenesulionyl chloride layer was washed Btim'es'in a 4-literI se arator-y funnel with'about 2 liters of water,

being al owed to stand overnight after the last wash. Residual wa er wasstripped of! the octyl I benzenesulfonyl chloride layer at atemperature.

of 70C. an under 5 mm. .Hg pressure. The de- I w tered distilland wasmixed with 270 grams of Retro! clay and filtered, representing a yieldon the octylbenzene starting or 71.6%, based product. I I C. Preparationof n-batyl octu lbenzenesaljonate n-Butanol in. the amount or 165 grams(2.25 mols) and 720 grams of a 50% NaOH solution (eouivalent to 9 molsof NaOH anhydrous basis) and 180 grams of water were combined in a 2liter 3 necked fiask e ui ped with a thermometer.

I ride addition was maintained intherange'of I 35.5-40 C. Additional'40%NaOH soluti'on'was then added to the esterification reaction mix- 'turein an amount sufficient to raise the total NaOI-I cohtent to a 12:1 molratio on the basis of octvlbenzenesulfonyl chloride starting product.The re: etion mixture was then transferred to an tt. i 2' liters fbenzene were added 8 liter ha M o 3 similarly to that previouslydescribed in Example and the mixture stirred for 2 hours at roomtemperature. There was then added 4 liters of wa-.- terand afterstanding for about 30'm'inutes the upper benzene layer separated out.The lower aqueous layer was drawn of! with a suction leg 40 was observedto be c ear and neutral. After a 45 period of st riding. residualbenzene was stri ed from the n-butvl octylhenzenesulfonate layer by disi ling at atmos heric pressure and then by warming'to 110 C. at 1-3 mm.Hg pressure.

benzenesultonate of the formula:

can -sor-cn.cmcmcm which had t e apnearanceof a clear brown oil. Th s reresented. a 79% theoretical yield based on octylbenzenesu fonyl chloridestarting product. The analysis of the n-butyl octylbenzenesulfonate v Iwas as follows:

Solubility: g.Ha0/100 g. compound at Theoretical 172. j

EXAMPLE 2 I A. Preparation of octfllbenzenesulfonylchloride-n-Octylbenzene prepared according to part .(A)- of Example 1, in theamount of 1,330 grams (7 mols) was'chlorsulfonated'with 2,440 grams ofchlorsulfon'ic acid (21 mols), the latter being I T 3.40am

added over a period of 68 minutes and the temring was continued for 22minut'esand the mix- 5. ture was then poured'onto approximately 4kilograms'of cracked ice, thereafter diluted with liters of tap water,and after standing for 30 minutes the upper aqueous layer was siphonedof! I and the remaining oily layer transferred to a 4 10 literseparatory funnel where it was washed 4 times with 1.5 liter portions ofwater, or until the g wash water was neutral. After standing overnight,the oily layer, having a slightly emulsified appearance, was thenstripped of water, employ- 5 ing a maximum distillation pot temperatureof 1 40 C. at a pressure or 5 mm. Hg pressure. There was obtained 1449.5grams of octylbenzenesulfonyl chloride product which was dark brown in jcolor. This product was then stirred at room temperature-with grams of"Retrol" clay and then filtered with Celite filter aid. There wasobtained 1457.5 grams of filtered, decolorized octylbenzenesulionylchloride representing a I '72.2 theoretical yield on the basis ofoctylben- 25 zene starting product.

B. Preparation of phem/l oetylbenzenesulfonate The octylbenzenesulfonylchloride obtained combined mixture of '640 grams of 50% NaOH solution (8mols), 160 grams of water (thereby adjusting NaOH concentration to 40%)and 262 grams (3 mols) of phenol, the latter mixture being contained ina 3 necked, 3 liter flask equipped 1 '(C). The octylbenzenesulfonylchloride addition was made over a period of 30 minutes, with stirring,-and such stirring was continued for an additional minutes, thetemperature being maintained in the range of 37-41" C. On transferringthe reaction mass to a 2 liter separatory funnel, from the bottom ofwhich a clear. light amber colored water soluble layer was drawn oil,the remaining oily layer was washed with 1 liter portions of tap wateruntil the pH of the wash water was reduced to 7.5. The crude phenylocwlbenzenesulfonate was then transferred to a 1-liter distilling flaskand dehydrated under re- There was Main, 490 grams of n buty1vocty1duced pressure. There was obtained 348 grams of dehydrated phenyloctylbenzenesulionate, of the formula:

1 cinir 400 representing an 81.6% theoretical yield based onoctylbenzenesulfonyl chloride starting product.

The phenyl octylbenzenesulionate had the fol-'- lowing analysis:

.lheoretical 162. I .I The n-butyl octylbenzenesulfonate product ofExample 1 and the phenyl octylbenzenesulfonate product of Example 2 weretested for plasticizing properties by being made up into a compositionof 2 parts of synthetic resin to 1 part of plasticizer,.such syntheticresin being polyvinyl ch10 I ride. Tests for plasticizingpropertiesshowed I v to a battery jar.

that these two octylbenzenesulfonate esters nossessed outstandingplasticizing properties of strength, low water absorption and lowvolatility. The test results are shown in the following table, where inorder to obtain a better appreciation, and to more easily comprehend thevalue of such plasticizing properties, corresponding figures are givenfor a polyvinyl chloride synthetic resin wherein the heretofore wellknown and outstanding plasticizing agent, di-2-ethylhexyl phthalateplasticizing agent has been employed as a control.

Preparation of phenyl maleaesulfonate Xylenesulfonyl chloride (1. e.di-methylbenzene sulfonyl chloride) in the amount of 689 grams, and of apurity of 94.5% (3.18 mols on 100% basis) were reacted with 3 54 grams(3.77 mols) of phenol and 1,219 grams of 40% NaOI-I (12 mols). Thexylenesulfonyl chloride was added over a period of 69 minutes, withcontinued'stirring for 46 minutes. The temperature varied from astarting temperature of 34 C. to 48 C. when all of the xylenesulfonylchloride was added.

The reaction mass consisted of 'a gummy light brown phase and anaqueouscloudy phase. The latter was poured oil and the remaining phase waswashed with 1 liter of water and transferred Thereupon 4 liters of waterwere added,the mass stirred andthe non-aqueous phase allowed to settle'out.. After withdrawal of the aqueous layer, the remaining prodmean? 6EXAMPLE 4 Preparation of n-butyl zylenesulfonate The ingredientsemployed for this synthesis were as follows:

xylcrz esulfonyl chloride (91.1% I

purity) 552.9 grams or 2.6 mols n-Butanol 220.9 grams or 3.0 molsCaustic soda, 40% concentration 1040 grams or 10.4 mols The caustic sodaand n-butanol were mixed and. cooled before adding the xylenesulfonylchloride. The reaction vessel employed was an enameled pail with a 4blade paddle type stirrer. The temperature was maintained in the rangeof 33-39 C. during the addition of all but the first 60cc. of thexylenesulfonyl chloride. The xylenesulfonyl chloride was'added over aperiod of 23 minutes, at which point the mixture was of a 'to a 1.5liter beaker and washed with 500 m1.

portions'of cold water until the wash water tested neutral. Some of theproduct was emulsified between the main portion and the aqueous layer,

uct layer which had an emulsion-like appearance waswashed repeatedlywith 1 liter portions of cold water. Acidic wash water containing about5 cc. of concentrated HCl per liter was then used, and after twowashings, the wash water tested neutral. The product phase ornon-aqueous phase was then filtered through "Celite" filter aid and thefiltrate distilled in a falling-film type of stripping still. A clear,brown colored product, phenyl xylenesulfonate' of the formula:

was obtained in the amount of 833 grams. :Ihis represented an 80% yieldbased upon the amount of xylenesulionyl chloridestarting product. Thephenyl xylenesulfonate product had the following analysis: Y 1

Saponification number 1 214.5

Negative 1 Theoretical 214.'

and this emulsified portion was twice put through 1 the falling-filmtype of dehydrating column yielding about 10 grams of amber brown oilproduct which was added to the main product portion of 465 grams, givinga total of 475 grams of product.

The yield of n-butyl xylenesulfonate of the chemical formula:

.C C4Hr-SO was 75.5% based on the xylenesulfonyl chloride startingproduct. its: analysis was as follows:

Saponification number (average of duplicate tests) 1 234 Specificgravity at 25 C. 1.117 Index of refraction at 25 C 1.5074

4 Theoretical 232. r

. EXAMPLE 5 Preparation of n-butyl sec.-butyl benzenesulfonate Theingredients employed in this synthesis were as follows: 1

Sec.-butyl benzenesulfonyl ch10- ride (94.3% purity) 761 grams or 3.1mols n-Butanoh 232'grams V v or 3.1 mols Caustic .soda (40%concentration) 12 grams or l2 nols The 'esterification reaction wasconducted in a manner similar to that employed in Example 4,

the see-{butyl benzenesulfonyl chloride being added over a period of 46minutes, followed by a continued stirring of the reaction mass for 43minutes. a After separation and water washing of the reactionproduct,followed by filtering through Celite and dehydration in the falling-filmtype of distillation column, there was obtained a 69.8%

aeaaerr ride starting product, of n-butyl sec.-butyl hen"-zenesulfonate' of the chemical formula:

. cnr-c'n-cm (am-so ester had the following analysis:

Preparation of phenyl sea-but!!! benzenesullonate The ingredientsemployed in this synthesis were as follows:

, carbon hydroxy compound is n-butanoi.

The sec.-butyl benzenesulfonyl chloride was added over aperiod of 41minutes, followed by continued stirring for a period of 33 minutes.

The maximum temperature of the reaction mass was observed to be 37 C.After water washing of the reaction mass, dehydration in the fallingfllmtype of still, there was obtained a 77.2% yield (based on sec.-butyibenzenesuifonyl chloride) of phenyl sec.-butyl benzenesulfonate of thechemical formula:

This product had the following analysis:

Saponificaton number (average of duplicate tests) 1 191 Specific gravityat 25% C. 1.612

Index of refraction at 25 C. 1.5498

- Theoretlcal 193.3.

Other modes of applying theprinciple of our invention may be employed,changes being made as regards to the details described, provided thefeatures stated in any of the following claims or Q the equivalent'ofsuch be employed- We, therefore, particularly point out. and dis.tinctly claim as ourinvention:

1. The process of reacting alkylbenzenesulfo-j nyl chloride with ahydroxy compound selected from the group consisting of normal aliphatical cohols, alkylene glycols, phenols and. homologues presence -50%caustic alkali, at a temperature of 35-50 0., said caustic alkali beingpres- -entin at least a 200% molar excess, and said hydrocarbon hydroxycompound being present. in

the amount of not over 2 mols per moi of alkyibenzenesulfonyl chloride.

. 2. The process or claim 1 wherein the hydro- 1 carbon hydroxy compoundis n-butanol.

3. The proeessiof claim 1 wherein the hydrocarbon hydroxy compound isphenol. 4. The process which consists in alkylating benzene with analkyl group containing-from 1 to a carbonatoms. chlorsuli'onating theresultant alkylbenzene, andv then reacting the city]- benzenesulfonyichloride with a hydroxy compound'selected from the group consisting ofnormai aliphatic alcohols, alkylene. glycols, phenols and homologues ofphenols, such reaction being conductedin the presence of 35-50% causticalkali, ata temperature of 3M0 Cssaid caustic alkali being present in atleast a 200% molar excess, and said hydrocarbon hydroxy compound beingpresent in the amount of not over 2 mols per mol ofalkylbenzenesulfonylchloride.

5. The process of claim -4 wherein the hydro- 6. I'heprocess'of claim 4wherein the hydrocarbon hydroxy compound. is phenol.

'l. The process which consists in alkylating benzene with an octylgroup, chlorsulfonating the resultant octylbenzene, treating the,octyibenzenesulfonyl chloride withclay and filtering, and then reactingthe octyibenzenesulfonyi chloride with -n-butanol in the presence of35-50% NaOH at a temperature of 35-50 C., the NaOH being present inapproximately a 1100% molar excess, and the n-butanol being present inan amount not over 2 mols per mol of octyibenzenesulfonyl chloride.

3.,The-process which consists in alkylating benzene with an octyl group,chlorsulfonating the resultant octylbenzene, treating the octyl-'benzenesulfonyl chloride with clay and filtering,

and then reacting the octylbenzenesuli'onyl of phenols, such reactionbeing conducted in the chloride with phenol in the presence of 35-50%NaIOH at ajtemperature of 35-50 C., the NaOH being presentin-approximately a 300% molar excess, andthe phenol being present in an'amountnot over-.2 mols sulfonyl chloride.

9. As a new chemical. compound, n-butyl octylbenzenesulfonate.

10. As a new chemical compound, phenyi octyll-enzenesulfonate. Y w 11.Octylbenzenesulfonic acid esters of the formula:

' ew -{De where'A' is a hydrocarbon radical selected from the groupconsisting of normal alkyl, phenyl and homologues of phenyl.

fnonALn R. JACKSON. WILLIAM K. LANGDON.

nnraimncns 1 The following references are of record in the file ofrmrrnns'ra'rns PATENTS Number Name Date 1,924,390, Cars'well Aug. 29,1933 2,017,803 Isham, Oct. 15, 1935 2327,7031 --Cordier Jan. 7, 19412,266,141 Adams Dec.18, 1941 3,340,101 'Schlichting et al. -Feb. 1, 1944per mol of octylbenzene-

